CN113845665A - Full-conjugated organic triazine framework material and preparation method and application thereof - Google Patents
Full-conjugated organic triazine framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 7
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- RXNOGMRZMCTLKA-UHFFFAOYSA-N benzene-1,4-dicarboxamide;hydrochloride Chemical compound Cl.NC(=O)C1=CC=C(C(N)=O)C=C1 RXNOGMRZMCTLKA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000004044 response Effects 0.000 abstract description 8
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
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- 238000009826 distribution Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
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- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 229910016523 CuKa Inorganic materials 0.000 description 2
- NUGPIZCTELGDOS-QHCPKHFHSA-N N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclopentanecarboxamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CC[C@@H](C=1C=NC=CC=1)NC(=O)C1CCCC1)C NUGPIZCTELGDOS-QHCPKHFHSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention provides a fully conjugated organic triazine framework material and a preparation method and application thereof, wherein sulfur element is doped in situ, the fully conjugated organic triazine framework material is doped and modified by the sulfur element, the in-situ doping of the sulfur element keeps the structure of the original crystalline state material to the greatest extent, electron cloud carriers in the sulfur element are obviously inhibited from being compounded, the radiation transition is reduced after photons are absorbed, the photocurrent response of the triazine framework material is further improved, and the efficiency of photocatalytic hydrogen production can be effectively improved when the sulfur element is used as a photocatalyst.
Description
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to a fully conjugated organic triazine framework material and a preparation method and application thereof.
Background
A fully conjugated organic Triazine skeleton (solvent Triazine Frameworks) is a class of fully conjugated organic Covalent skeleton materials containing Triazine rings. Due to the unique topological structure and the electron cloud distribution, the material has the advantages of wider sideband absorption, high carrier mobility, good thermal stability and the like, and is widely applied to the fields of photocatalysis, photodynamic and the like. However, the full-conjugated organic triazine skeleton has high electron cloud carrier recombination rate due to good planarity, so that the full-conjugated organic triazine skeleton has obvious radiation transition after absorbing photons and small photocurrent response, and the photocatalytic hydrogen production efficiency is low.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the novel full-conjugated organic triazine framework material is provided, the electron cloud carrier recombination rate in the full-conjugated organic triazine framework material can be effectively inhibited, meanwhile, the completeness of the pore channels in the framework material is greatly kept, the carrier mobility is further improved, and the photocatalytic hydrogen production efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a fully conjugated organic triazine skeleton material is doped with sulfur element in situ, the chemical structural formula of the fully conjugated organic triazine skeleton material is shown as formula 1,
according to the invention, sulfur element is adopted to dope and modify the full-conjugated organic triazine framework material, the in-situ doping of the sulfur element maintains the structure of the original crystalline material to a great extent, and the electron cloud carriers in the sulfur element are obviously inhibited from being compounded, so that the radiation transition is reduced after the photons are absorbed, the photocurrent response of the triazine framework material is further improved, and the efficiency of photocatalytic hydrogen production can be effectively improved when the triazine framework material is used as a photocatalyst.
Preferably, the doping rate of the sulfur element is 0.1-20%. More preferably, the doping rate of the sulfur element is 5 to 15%. More preferably, the doping ratio of the sulfur element is 10%. Proper amount of sulfur element doping can effectively redistribute the electron cloud distribution in the framework material, so that the separation rate of carriers in the electron cloud is improved, and the efficiency of photocatalytic hydrogen production is improved.
The second purpose of the invention is to provide a preparation method of the fully conjugated organic triazine framework material, which comprises the following steps:
s1, reacting the ammonium sulfide aqueous solution with terephthalonitrile to prepare thio-terephthalamide;
s2, mixing the thioterephthalamide obtained in the step S1 with terephthalamide hydrochloride and terephthalaldehyde, and preparing the sulfur-doped fully conjugated organic triazine framework material under the action of an alkaline catalyst.
Preferably, in step S1, the preparation method of the thioterephthalamide includes: adding a solvent into terephthalonitrile to completely dissolve the terephthalonitrile, then adding a 15 wt% ammonium sulfide aqueous solution under the protection of an inert atmosphere, and stirring for reacting for 24 hours; and after the reaction is finished, pouring the reaction liquid into deionized water, filtering, extracting the filtrate, drying the organic phase in the filtrate by using anhydrous sodium sulfate, and spin-drying the solvent to obtain a yellow solid, wherein the yellow solid is purified by column chromatography and then is combined with the filter cake for drying to obtain the thioterephthalamide.
Preferably, in step S1, the inert atmosphere is nitrogen and/or argon; the solvent for extraction is at least one of ethyl acetate, dichloromethane and chloroform.
Preferably, in step S1, the column chromatography is performed by 300-400 mesh silica gel column chromatography, and the volume ratio is 1: 1 petroleum ether and ethyl acetate as eluent.
More preferably, the preparation method of the thioterephthalamide comprises the following steps: adding 1 molar equivalent of terephthalonitrile (namely compound 1) into a round-bottom flask at normal temperature, then adding N, N-dimethylformamide or dimethyl sulfoxide to completely dissolve the solid, then slowly adding 3-5 molar equivalents of 15 wt% ammonium sulfide aqueous solution under the protection of inert gas, and stirring at room temperature for 12-24 hours. And after the reaction is finished, pouring the reaction liquid into deionized water with 50 times of volume equivalent, filtering, extracting the filtrate by using an extracting agent, drying an organic phase by using anhydrous sodium sulfate, carrying out spin drying on the solvent to obtain a yellow solid, purifying the yellow solid by using column chromatography, and then combining the yellow solid with a filter cake and drying to obtain the thioterephthalamide (namely the compound 2). The specific synthetic route is as follows:
preferably, in step S2, the preparation method of the fully conjugated organic triazine skeleton material comprises: adding thioterephthalamide, terephthalamide hydrochloride, terephthalaldehyde and an alkaline catalyst into a reactor, adding a solvent, heating to 80-85 ℃ for reaction for 10-12 h, then heating to 100-105 ℃ for continuous reaction for 10-12 h, then heating to 120-125 ℃ for reaction for 24-30 h, cooling to room temperature, adding dilute hydrochloric acid, filtering, washing and precipitating, and drying at 60-85 ℃ in vacuum to obtain the sulfur element doped fully conjugated organic triazine framework material.
Preferably, in step S2, the basic catalyst is cesium carbonate or potassium carbonate; the concentration of the dilute hydrochloric acid is 3-6 mol/L.
In order to determine the chemical environment of the S element in the porous material, the invention synthesizes a compound 6 by using the following compounds 3-5 and a similar method, wherein the reaction path is as follows:
the preparation method comprises the following steps: adding 1 mol equivalent of a compound 4 into a round-bottom flask at normal temperature, then adding 1.1-1.5 mol equivalents of a compound 5 and 2 mol equivalents of a compound 3, then adding 2 mol equivalents of a catalyst and 10-20 times of dimethyl sulfoxide or N, N-dimethylformamide of the compound 4, reacting for 10-12 hours at 80-85 ℃, then reacting for 10-12 hours at 100-105 ℃, and finally reacting for 24-30 hours at 120-125 ℃. And cooling to room temperature, dropwise adding dilute hydrochloric acid with the volume equivalent of 5-10 times into the system, filtering, washing the precipitate, and purifying the residue by using column chromatography to obtain the compound 6. Wherein the column chromatography adopts 200-300 mesh silica gel column chromatography, and adopts a volume ratio of 1: 100 parts of methanol and dichloromethane are used as eluent.
More specifically, the preparation method of the fully conjugated organic triazine framework material comprises the following steps: adding 1 molar equivalent of terephthalmidine hydrochloride (compound 7), 0-0.2 molar equivalent of thioterephthalamide (compound 2), 1-1.5 molar equivalent of terephthalaldehyde (compound 8) and 2 molar equivalent of an alkaline catalyst into a round-bottomed flask at room temperature, adding 10-20 times of dimethyl sulfoxide or N, N-dimethylformamide by mass of the compound 8, heating the reaction solution to 80-85 ℃ for reaction for 10-12 hours, heating to 100-105 ℃ for reaction for 10-12 hours, finally reacting at 120-125 ℃ for 24-30 hours, cooling to room temperature, dropwise adding 5-10 times of volume equivalent of dilute hydrochloric acid into the system, filtering, washing and precipitating, and drying at 60-85 ℃ overnight under vacuum to obtain the fully conjugated organic triazine framework material (compound 9). The specific synthetic route is as follows:
the invention also aims to provide the application of the fully conjugated organic triazine framework material in photocatalysis.
The invention has the beneficial effects that:
1) according to the fully conjugated organic triazine framework material provided by the invention, sulfur element is introduced into a framework of the framework material by in-situ doping, and sulfur atom groups rich in an electron p track can redistribute electron cloud distribution in the organic triazine framework material, so that the separation rate of carriers in the electron cloud is improved. In addition, the sulfur atom can also form a chemical bond with a platinum-series co-catalyst for photocatalytic hydrogen production, so that the effect of dispersing the co-catalyst is achieved, and the photocatalytic hydrogen production efficiency can be further improved.
2) Compared with the method of directly mixing the prepared framework material with the simple substance of the heteroatom element and replacing part of atoms in the framework by the heteroatom at high temperature, the preparation method of the framework material provided by the invention adopts an in-situ doping method, so that not only can doping modification be carried out under a mild condition, but also the pore passage in the framework material can be kept better, and the doped sulfur element can be adjusted and controlled, and the preparation method is simpler.
Drawings
Fig. 1 is a steric structure diagram of a simulated in-situ sulfur-doped fully conjugated organotriazine skeleton, wherein 1 and 2 in the diagram respectively represent two adjacent sulfur atoms.
FIG. 2 is X-ray diffraction patterns of the fully conjugated organic triazine skeletons of examples 1-2 of the present invention and comparative example 1, wherein A denotes comparative example 1, B denotes example 2, and C denotes example 1.
FIG. 3 is a steady state fluorescence spectrum of the fully conjugated organic triazine skeletons of examples 1-2 and comparative example 1 of the present invention, wherein A denotes comparative example 1, B denotes example 2, and C denotes example 1.
FIG. 4 is a graph showing photocurrent response of fully conjugated organotriazine skeletons of examples 1-2 and comparative example 1 of the present invention, wherein A is comparative example 1, B is example 2, and C is example 1.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a fully conjugated organic triazine framework material comprises the following steps:
1) synthesis of Compound 2: at room temperature, compound 1(2.56g,20mmol) was added to a round bottom flask, then 50mL of N, N-dimethylformamide was added to dissolve the solid completely, then a certain amount of 15 wt% aqueous ammonium sulfide solution (40mL, 80mmol) was added slowly under argon protection and stirred at room temperature for 12 hours. After the reaction is finished, pouring the reaction liquid into 2500mL of deionized water, filtering, extracting the filtrate by 1000mL of ethyl acetate, drying the organic phase by using anhydrous sodium sulfate, and spin-drying the solvent to obtain a yellow solid, purifying the yellow solid by using 300-mesh 400-mesh silica gel column chromatography (petroleum ether/ethyl acetate: 1/1), and then combining the yellow solid with a filter cake and drying to obtain 3.79g of a compound 2 (thioterephthalamide), wherein the yield is 94.5%. For the resultant product1HNMR(DMSO-d6400MHz) was used for characterizationThe following data were obtained: deltaH 10.01(s,2H),9.61(s,2H),7.83(m,4H)。
2) Synthesis of Compound 6: compound 4(1mL, 10mmol) was added to a round-bottom flask at room temperature, followed by addition of Compound 5(1.51g, 11mmol) and Compound 3(3.48g, 20mmol), followed by addition of cesium carbonate as a basic catalyst (6.51g, 20mmol) and 20mL of dimethyl sulfoxide as a reaction solvent, followed by reaction at 85 ℃ for 12 hours, followed by reaction at 105 ℃ for 12 hours, and finally at 125 ℃ for 24 hours. After cooling to room temperature, 100mL of 3mol/L diluted hydrochloric acid was added dropwise to the system, the precipitate was washed with dimethyl sulfoxide, water and ethanol after filtration, and the residue was purified by 200-mesh 300-mesh silica gel column chromatography (methanol/dichloromethane: 1/100) to obtain 757mg of compound 6 with a yield of 23%. For the resultant product1HNMR(DMSO-d6400MHz) to obtain the following data: deltaHδ7.80(m,2H),7.71(m,2H),7.57–7.43(m,6H),7.34(m,2H),7.37–7.27(m,3H),6.69(s,1H)。
3) Synthesis of compound 9: compound 7(3.58g, 18mmol), compound 2(0.28g, 2mmol), compound 8(1.34g, 10mmol) and cesium carbonate as a basic catalyst (6.51g, 20mmol) were charged into a round-bottomed flask at room temperature, 20mL of dimethyl sulfoxide as a reaction solvent was further added, and the mixture was reacted at 85 ℃ for 12 hours, then at 105 ℃ for 12 hours and finally at 125 ℃ for 24 hours. After cooling to room temperature. After cooling to room temperature, 50mL of 6mol/L dilute hydrochloric acid was added dropwise to the system, and after filtration, the precipitate was washed with dimethyl sulfoxide, water and ethanol, and dried overnight at 60 ℃ under vacuum to give 4.26g of Compound 9 (fully conjugated organotriazine skeleton material) having 5% sulfur content, with a yield of 87%. The resulting product was characterized by X-ray diffraction (CuKa) to obtain the following data: diffraction peak position: 8.2 ° and 24.5 °.
The sulfur doping amount of the fully conjugated organotriazine skeleton material obtained in this example was 10%.
Example 2
A preparation method of a fully conjugated organic triazine framework material comprises the following steps:
1) process for preparation of Compound 2Synthesizing: at room temperature, compound 1(1.28g,10mmol) was added to a round bottom flask, then 50mL of N, N-dimethylformamide was added to dissolve the solid completely, then a certain amount of 15 wt% aqueous ammonium sulfide solution (25mL, 50mmol) was added slowly under argon protection and stirred at room temperature for 12 hours. After the reaction is finished, the reaction liquid is poured into 1000mL of deionized water, filtration is carried out, 500mL of ethyl acetate is used for extracting filtrate, an organic phase is dried by anhydrous sodium sulfate, a yellow solid is obtained by spin-drying a solvent, and the yellow solid is purified by 300-mesh 400-mesh silica gel column chromatography (petroleum ether/ethyl acetate: 1/1) and then is combined with a filter cake for drying, so that 1.95g of the compound 2 (thioterephthalamide) is obtained, and the yield is 97.3%. For the resultant product1HNMR(DMSO-d6400MHz) to obtain the following data: deltaH10.02(s,2H),9.59(s,2H),7.81(m, 4H). It can be seen that it compares to example 11The peak positions of HNMR are similar, and the integral areas are consistent, which shows that the method can also obtain the purer compound 2.
2) Synthesis of Compound 6: compound 4(1mL, 10mmol) was added to a round-bottom flask at room temperature, followed by addition of Compound 5(1.51g, 11mmol) and Compound 3(3.48g, 20mmol), followed by addition of cesium carbonate as a basic catalyst (6.51g, 20mmol) and 20mL of dimethyl sulfoxide as a reaction solvent, followed by reaction at 85 ℃ for 12 hours, followed by reaction at 105 ℃ for 12 hours, and finally at 125 ℃ for 24 hours. After cooling to room temperature, 80mL of 5mol/L dilute hydrochloric acid was added dropwise to the system, the precipitate was washed with N, N dimethylformamide, water and ethanol after filtration, and the residue was purified by 200-mesh 300-mesh silica gel column chromatography (methanol/dichloromethane: 1/100) to obtain 592mg of compound 6 with a yield of 18.2%. For the resultant product1HNMR(DMSO-d6400MHz) to obtain the following data: deltaH7.78(m,2H),7.73(dd,2H), 7.57-7.43 (m,6H),7.32(m,2H), 7.36-7.29 (m,3H),6.40(s, 1H). It can be seen that it compares to example 11The peak positions of HNMR are similar, and the integral areas are consistent, which shows that the method can also obtain the purer compound 6.
3) Synthesis of compound 9: compound 7(3.58g, 18mmol), compound 2(0.28g, 2mmol), compound 8(1.34g, 10mmol) and cesium carbonate as a basic catalyst (6.51g, 20mmol) were charged into a round-bottomed flask at room temperature, 20mL of dimethyl sulfoxide as a reaction solvent was further added, and the mixture was reacted at 85 ℃ for 12 hours, then at 105 ℃ for 12 hours and finally at 125 ℃ for 24 hours. After cooling to room temperature. After cooling to room temperature, 50mL of 6mol/L dilute hydrochloric acid was added dropwise to the system, and after filtration, the precipitate was washed with dimethyl sulfoxide, water and ethanol, and dried overnight at 60 ℃ under vacuum to give 4.26g of compound 9 with 5% sulfur content, in 87% yield. The resulting product was characterized by X-ray diffraction (CuKa) to obtain the following data: diffraction peak position: 7.9 ° and 24.3 °. It can be seen that this is a crystalline material as compared with example 1, indicating that compound 9 having crystallinity can be obtained by this method as well.
The sulfur doping amount of the fully conjugated organotriazine skeleton material obtained in this example was 20%.
Comparative example 1
The preparation method of the fully conjugated organic triazine framework material obtained in the comparative example is obtained by a conventional preparation method, is not doped with sulfur, is the same as that in example 1, and is not repeated herein.
The performance tests of the fully conjugated organic triazine framework materials obtained in the embodiments 1-2 and the comparative example 1 include an X-ray diffraction test, a steady-state fluorescence spectrum test and a photocurrent response test, which can be shown in FIGS. 2-4.
As can be seen from fig. 2 to 4, after the fully conjugated organic triazine framework material is doped with sulfur, the steady-state fluorescence of the molecules is lower and the photocurrent response value is larger compared with that of the undoped framework material, so that the integrity of the pore channels in the framework material is greatly maintained after the S doping, the electron cloud carrier recombination rate in the fully conjugated organic triazine framework material is effectively inhibited, the radiation transition is reduced after the photons are absorbed, and the photocurrent response of the triazine framework material is further improved.
The fully conjugated organic triazine framework material is continuously used as a catalyst to be applied to photocatalysis to test the hydrogen production performance, and the test result is shown in table 1.
TABLE 1
From the results, the fully conjugated organic triazine framework material doped with the S element also effectively improves the photocatalytic hydrogen production performance, and corresponds to the X-ray diffraction test, the steady-state fluorescence spectrum test and the photocurrent response test. In addition, the results can also show that when the proportion of the doped S element is 10%, the performances of the fully conjugated organic triazine framework material are improved better.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. The fully conjugated organic triazine framework material is characterized in that sulfur element is doped in situ, the chemical structural formula of the fully conjugated organic triazine framework material is shown as a formula 1,
2. the fully conjugated organotriazine skeleton material of claim 1, wherein the doping ratio of the sulfur element is 0.1 to 20%.
3. The preparation method of the fully conjugated organic triazine framework material is characterized by comprising the following steps of:
s1, reacting the ammonium sulfide aqueous solution with terephthalonitrile to prepare thio-terephthalamide;
s2, mixing the thioterephthalamide obtained in the step S1 with terephthalamide hydrochloride and terephthalaldehyde, and preparing the sulfur-doped fully conjugated organic triazine framework material under the action of an alkaline catalyst.
4. The method of preparing a fully conjugated organotriazine skeleton material of claim 3, wherein in step S1, the method of preparing thioterephthalamide is: adding a solvent into terephthalonitrile to completely dissolve the terephthalonitrile, then adding a 15 wt% ammonium sulfide aqueous solution under the protection of an inert atmosphere, and stirring for reacting for 24 hours; and after the reaction is finished, pouring the reaction liquid into deionized water, filtering, extracting the filtrate, drying the organic phase in the filtrate by using anhydrous sodium sulfate, and spin-drying the solvent to obtain a yellow solid, wherein the yellow solid is purified by column chromatography and then is combined with the filter cake for drying to obtain the thioterephthalamide.
5. The method for preparing a fully conjugated organotriazine skeleton material of claim 4, wherein in step S1, the inert atmosphere is nitrogen and/or argon; the solvent for extraction is at least one of ethyl acetate, dichloromethane and chloroform.
6. The method for preparing the fully conjugated organic triazine framework material as claimed in claim 4, wherein in the step S1, the column chromatography is performed by 300-400 mesh silica gel column chromatography, and the volume ratio is 1: 1 petroleum ether and ethyl acetate as eluent.
7. The method of producing a fully conjugated organotriazine skeleton material according to any one of claims 3 to 6, wherein in step S2, the method of producing the fully conjugated organotriazine skeleton material comprises: adding thioterephthalamide, terephthalamide hydrochloride, terephthalaldehyde and an alkaline catalyst into a reactor, adding a solvent, heating to 80-85 ℃ for reaction for 10-12 h, then heating to 100-105 ℃ for continuous reaction for 10-12 h, then heating to 120-125 ℃ for reaction for 24-30 h, cooling to room temperature, adding dilute hydrochloric acid, filtering, washing and precipitating, and drying at 60-85 ℃ in vacuum to obtain the sulfur element doped fully conjugated organic triazine framework material.
8. The method for preparing a fully conjugated organotriazine skeleton material of claim 7, wherein in step S2, the basic catalyst is cesium carbonate or potassium carbonate; the concentration of the dilute hydrochloric acid is 3-6 mol/L.
9. Use of a fully conjugated organotriazine framework material according to claim 1 or 2 in photocatalysis.
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